Esters of piperonyl chrysanthemum carboxylic acid



Patented Jan. 11, 1949 ESTERS F rlraaomu. CHRYSANTHEMUM CARBOXYLIC ACID 1 Martin E.

Synerholm, Hastings onHudson, N. Y.,

assignor to Boyce Thompson Institute for Plant Research, 1nc., a corporation of New York No Drawing. App] ication March as, 1946,

, Serial No. 657,349

This invention relates to organic compounds and has for its object the provision of a new compound and insecticidal compositions comprising the new compound. The new compound of, my invention is the plperonyl ester of chrysanthe mum carboxylic acid (2,2-dimethyl-3-isobutenyl cylcopropane-l-carboxylic acid). This compound maybe prepared from piperonyl alcohol and chrysanthemum carboxylic acid. The chrysanthemum carboxylic acid may be derived as a natural product from plants, for example, from Chrysanthemum cinerariifolium Bocc., or it may be prepared synthetically. The compound derived from plants is largely or wholly the d-trans isomer, while the synthetic compound is a mixture of several isomers, d,l-cis and d,l-trans acids.

I have made the significant discovery that the synthesized mixture of four isomer d,l-cis, and d,l-trans acids is equally as efiective as the d-trans isomer from pyrethrins from the plant Chrysanthemum cinerariifolium occurring naturally and that it is, accordingly, not necessary to separate the isomers to produce an ester from separate isomers. The synthesized mixture may be made by starting with methallylchloride from which 2,5-dimethylhexadiene-1,5 is prepared. This compound is isomerized to 2,5-dimethyl-hexadicue-2,4 which, with diazo-acetic ester, yields the ethyl ester of chrysanthemum carboxylic acid. This ester is saponifled to the free acid. There is practically no difference in effectiveness, when tested againsthouseflies (M usca domestica) in the large group Peat-Grady chamber, between the isomeric mixture of synthetic origin and the 3 Claims. (Cl. 260- 38) The piperonyl alcohol may be obtained by reduction of piperonal, an oxidation product of isosafrol or.. other a-B unsaturated 3-4 methylene dioxyphenyl compounds.

namely, the four isomeric The piperonyl ester of my invention may be synthesized by adding piperonyl alcohol to an equivalentamount of the acid chloride of claimsanthemum carboxylic acid prepared by the action of thionyl chlorlde'or other chlorinating agent on the acid in any suitable form such as; the d-Ltrans isomer from the flowers or the mixture of d,l-cis and d,l-transacids prepared synthetically. The ester may be prepared by any other means of effecting esterification. v

The compounds of the invention are readily soluble in the petroleum distillates commonly used as solvents in insecticidal sprays, such as Dec-Base. They may be incorporated in powders such as talc to form insecticidal dusts, or used as mists or aerosols. The compound of the invention may be mixed with pyrethrins, plperine, or'DDT to produce compositions exhibiting synergism.

Spray-solutions containing the compounds of the invention were tested against housefiies by-the large Group Peet-Grady Method ("Blue Book" pp. 177-181, McNair-Dorland Co., New York. 1939). Control tests with the Omcial Test Insecticide (0T1) (Soap and Sanitary Chemicals 21 (6) 137, 141, June, 1945), which containsapproximately 0.1 g. of pyrethrins per 100 ml., also were carried out on each batch of flies used. The compound was dissolved in Dec-Base, a purified petroleum distillate Table vI describes the materials'and quantities used and the results. of the tests:

Table I Derivative oi Chrysanthemum Carboxyiio G. per g DDT Per Cent Per Cent r 100 Knock- Per Cent Add mo m l Km down Kill Plperonyl ester (irom d-trans acid) 95 44 D0 93 97 53 76 m 66 95 49 4t) 52 93 so 95 95 I3" 82 85 52 79 86 ill ester prepared irom the d-trans acid obtained from a plant source.

Table IIillustratesthe similar effectiveness of the compounds/formed oil thenatural and the synthetic chrysanthemnm carbozq'lic acids when I claim: used with piperine: 1. The compound piperonyl ester 2,2-di- Table II Derivative of G G H in re cent Per cent 0. '1. I. Chr santhemum W r Knock- Per cent Car%oxyiic Acid m down Kill Piporonyl ester-natural. 0. 5 0. 94 96 58 Piperonyl ester-synthetic-.. 0. 5 0. 25 90 92 63 Piperonyl latch-natural..." 0. 25 0. 125 72 92 53 Piperonyl ester-synthetic. 0. 25 0. 125 73 82 53 Piperonyl esternatural.. 0.25 0. 125 77 93 61 Piperonyl ester-synthetic. 0. 25 0. 125 84 89 61 Tests with the piperonyi ester of chrysanthemum carboxyiic. acid on Aphis rumicis on nasturtium plants were carried out with water sprays using sodium lauryl sulfate as an emulsi- The same spray composition, used in the tests of Table III, was used on pea-aphid on broad bean plants with the results shown in Table IV:

Table IV Per cent No. No. Total Concentration of Ester Dead Alive Insects mi;

methyl-3-isobutenyl cyclopropane-i carboxylic acid.

2. An insecticidal composition comprising the ester of piperonyl alcohol and the d-trans isomers of chrysanthemum carboxylic acid.

3. An insecticidal composition comprising the ester of piperonyl alcohol and the d,l-cis and d,ltrans isomers of Chrysanthemum carboxylic acid.

MARTIN E. SYNERHOLM.

REFERENCES CITED The following references are of record in the tile of this patent:

West: Chemistry an Industry August 5 1944, pages 290 to 294. 

